Derivatives of perfluorated carboxylic acids

ABSTRACT

RT-CONH-(CH2)3-N(CH2CH2O)NH)2(R)X&amp;,   IN WHICH N IS A NUMBER FROM 1 TO 4, Z IS 1 OR 2, R REPRESENTS A LOWER ALKYL GROUP AND X- IS A HALOGEN SULFATE OR METHOSULFATE ANION, AND PROCESS FOR PREPARING THESE COMPOUNDS, WHEREIN PERFLUORO-ALKANE-CARBOXYLIC ACID ALKYL ESTERS, ARE REACTED WITH 1-(N,N-DIETHANOL)-3AMINO-PROPANE AND , DEPENDING ON THE COMPOUND, SUBSEQUENTLY OXETHYLATED, ESTERIFIED AND/OR QUATERNIZED. THE NEW COMPOUNDS STRONGLY REDUCE THE SURFACE TENSION OF AQUEOUS SOLUTIONS. THEY HAVE AN EXCELLENT WETTING POWER AND MAY ALSO BE USED AS EMULSIFIERS FOR FLUORO-HYROCARBON/WATER EMULSIONS. SURFACE-ACTIVE PERFLUORATED ALKANE-CARBOXYLIC ACIDAMIDE-AMINE DERIVATIVES AND THEIR QUATERNIZATION PRODUCTS OF THE FORMULAE   D R A W I N G RT-CONH-(CH2)3-N(CH2CH2O)NH)2)(CH2)5C O O&amp;),   RT-CONH-(CH2)3-N(CH2CH2O)NH)2,

United -States Patent Oce 3,836,552 Patented Sept. 17, 1974 3,836,552DERIVATIVES F PERFLUORATED CARBOXYLIC ACIDS Haus Stach, Suzano SaoPaulo, Brazil, and Dieter Hoffmann, Burghausen, Salzach, and HeinzBrecht, Burg, Germany, assignors to Farhwerke HoechstAktiengesellschaft, Frankfurt am Main, Germany Filed May 31, 1972, Ser.No. 258,365 Claims priority, application Germany, June 2, 1971, I 21 27232.2 Int. Cl. C07c 103/30 U.S. Cl. 26o-404.5 4 Claims ABSTRACT OF THEDISCLOSURE Surface-active peruorated alkane-carboxylic acidamide-aminederivatives and their quaternization products of the formulae Rf-CONH-(CH2)3-N[(CH2CH20)H]2,

, The present invention provides surface-active perurated carboxylicacid-amidamine derivatives and their quaternization products of thegeneral formula RCONH CH2) aY in which Rf represents an unbranchedperlluoro-alkyl group of 6 to 10 carbon atoms and Y represents a groupof the formula N[(CH2CH20)H]2 in which n=l4, tz=12, R represents loweralkyl and X represents halogen, sulfate or methosulfate, and a processfor preparing them.

German Patents 1,006,427 and 1,006,426 describe processes for lthemanufacture of surface-active carboxylic acid-amidamine derivativeswhich correspond to the general formulae R RfCONH(CH2)mN and 9/ R, coNmoHamNR'fA@ in which Rf represents a peruoro-alkyl group having 3-11carbon atoms, m represents a whole number of 2 to y6, R, R' and R"represent alkyl groups having 1 to 6 carbon atoms and R'" represents lacarboxyor dicarboxy-alkylene group and A- represents an anion.

In the technical use of uoro-tensides it is desirable to apply them inas low quantities as possible, i.e. they should have a strong actionalready when applied in low concentrations. 'I'he not-quatemizedcompounds described above have the disadvantage of being too sparinglysoluble in water to produce a strong reduction of the surface tension.The quaternized compounds described above have a good solubility, but inorder to produce a strong reduction of the surface tension they must beapplied in relatively high concentrations.

The compounds prepared according to the present invention largely avoidthese disadvantages, because the introduction of the alkylol groups, andstill more their subsequent oxethylation, increases the water-solubilityof the not-quaternized compounds, without affecting the solubility inorganic solvents, to such an extent that a strong reduction of thesurface tension is obtained when they are used in water. The surfaceactivity of the aqueous solutions of the quaternized compounds of theinvention is also considerably higher than that of the correspondingafore-descrbed alkyl compounds. This was clearly proved by the series dRfCONH(CH2)3N(CHzCHgOIEDzCHgCHzCOO' an R(CONH(CH2)3*N(CH3)3CH2 H2000'(lll Rf=C6F13-, C7F15 031.717'- alld C9F19`) k(cf. Table 1 and FIG. land FIG. 2, which show function curves of the surface tension (dyn/cm.)of aqueous solutions in dependence of the concentration |(in grams ofsubstance per liter of solution) Thus, with the quaternizedalkylol-groups containing compounds essentially smaller quantities arerequired for obtaining the same reductions of the surface tension (up toas with analogous alkyl-groups containing substances.

The compounds of the invention are prepared as follows: the reaction ofperuoro-carboxylic acid alkyl esters withN,Ndiethyloltrimethylenediamine yields peruorocarboxylic acidamido-trimcthylene-dialkylolamines of the formula These reactionproducts have differently reactive centers, namely the OH-groups and theamine nitrogen. The alkylo1 groups may be, for example etheried oresterified, the amine nitrogen may be quaternized. Suitable ethericationagents are ethyleneor propylene oxide, suitable esteriication componentsare acrylic acid, methacrylic acid, sulfuric acid, suitable quaternizingagents are alkyl halides, dimethyl sulfate, chloroacetic acid, lactonesand sultones.

The perfluoro-alkyl carboxylic acid amido-trimethylenediethylolamines,their oxalkylates and their quaternization products are suitable forstrongly reducing the surface tension in aqueous systems already whenapplied in low concentrations.

Aqueous solutions have an excellent wetting power, especially 'atelevated temperature. This was proved on textile material `according tothe DIN test 53,901 (German Industrial Standard) for the determinationof the immersion wetting power (cf. Table 2). At the same time, thesuperior wetting power of the aqueous solutions of the dialkylolcompounds of the invention Ias compared to that of analogous dialkylcompounds is remarkable.

The compounds of the invention may also be used as emulsiilers. Theremay be prepared with them, for example fluoro-hydrocarbon/wateremulsions which have industrial importance in the field of cleaning oftextile materials, metallic and non-metallic industrial materials.

The following Examples illustrate the invention:

EXAMPLE l 100 g. of peruoro-octanoic acid ethyl ester were dissolved in100 ml. of ether and rinsed with an inert gas. 33 g. oftrimethylene-diamine-N,Ndiethanol were added dropwise, while stirring,at -5 C., within 4 hours. The whole was then stirred for 3 hours at roomtemperature. Ether and alcohol were then removed on a rotary evaporatorat a bath temperature of 70 C. A colorless oil remained. The yield was123 g. 100%) of product having a purity of 98.5% (gas chromatogram).

C7F15CONH(CH2)3 percent total base-N: 2.51; see-Hert. N: 2.51; percenttert. N: 2.51. Found: total base-N: 2.52; sec.+tert. N: 2.43; percenttert. N: 2.43.

In a second experiment carried out in a manner analogous to that of theabove-described preparation, 800 g. of peruoro-octanoic acid ethyl esterwere dissolved in 500 ml. of ether and reacted with 293 g. oftrimethylenediamine-N,Ndiethanol. When the reaction was completed, thesolvent was not removed, but 132 g. of propiolactone were addeddropwise, while stirring, at room temperature. The whole was then boiledfor 6 hours under reflux. Ether and alcohol were then removed at 60 C.on a rotary evaporator. 1100 g. (96.2% of the theory) of a colorless oilremained.

Calc: percent C, 34.3; percent F, 45.1; percent H, 3.4; percent N, 4.4.Found: percent C, 34.6; percent F, 43.9; percent H, 3.5; percent N, 4.3.

EXAMPLE 2 50 g. and 90 g., respectively, of perfluoro-octanoicacidamido-trimethylene-N,Ndiethanolamine were introduced together with0.1 g. and 0.3 g., respectively, of sodium methylate into an autoclaveprovided with a stirring device and heated to 100 C. At thistemperature, 13 g. and 47 g., respectively, of ethylene oxide wereintroduced under pressure at this temperature in the course of hours. Aviscous liquid formed, 30 g. and 27 g., respectively, of the aboveoxethylates were placed in a stirring ask and 3 g. and 2.3 g.,respectively, of propolactone were added dropwise wthin l5 minutes.During that time the temperature rose by some degrees. The whole wasstirred for 2 hours, whereafter 27 g. and 24 g., respectively, ofviscous oils were obtained, the ethylene oxide contents of which(according to Obruba) were found to be 2.0 and 7.2 mols, respectively.

EXAMPLE 3 20 g. of CGFBCOOEt, C8F17COOEt, CQFIQCOOEt and CmFmCOOEt,respectively, were diluted with each time 150 ml. of ether and 12.4 g.,11.0 g., 9.0 g. and 5.8 g., respectively, oftrimethylene-diamineN,N-diethanol were added dropwise, While stirring,in the course of 30 minutes, to these dilutions. The batches werestirred for 3 hours at 25 C. Then, 5.5 g., 4.4 g., 4.0 g. and 2.5 g.,respectively, of propiolactone were added dropwise at the sametemperature. The batches were boiled for 3 hours under reflux. Ether andethanol were removed on a rotary evaporator while slowly heating to 50C. Viscous colorless oils were obtained in almost quantitative yields.

Calc: percent C, 35.2; percent F, 42.6; percent H, 3.6; percent N, 4.8.Found: percent C, 35.3; percent F, 42.7; percent H, 3.8; percent N, 4.7.

Calc: percent C, 33.5; percent F, 47.5; percent H, 311;

rpercent N, 4.1. Found: percent C, 33.5; percent F, 45.6; percent H,3.6; percent N, 4.5.

Calc: percent C, 32.9; percent F, 49.4; percent H, 2.9; percent N, 3.8.Found: percent C, 32.7; percent F, 47.9; percent H, 2.9; percent N, 3.9.

Calc: percent C, 32.3; percent F, 51.2; percent H, 2.7; percent N, 3.6.Found: percent C, 31.3; percent F, 47.3; percent H, 3.0; percent N, 4.4.

EXAMPLE 4 150 g. of

EXAMPLE 5 Small circular pieces of a cotton fabric were prepared inaccordance with DIN 53,901 (German Industrial Standard) and the .sinkingtimes in aqueous tenside solutions at different concentration andtemperatures were determined according to the indicated standard testprocess. The corresponding concentrations for a sinking time of secondswere determined graphically. The results are shown in Table 2.

EXAMPLE 6 The quaternization products were found to be suitable forpreparing water-in-fiuorohydrocarbon emulsions.

The attempt was made to prepare a stable emulsion of 5% of water intrilluoro-trichloro-ethane. Two emulsiers used in the art for such lapurpose were tested in the following quantities:

Percent of Percent'l of emulsiter I 1 emulsier II l 3. 0 2. 0 Stablesolubilized emulsion. 1. 5 1.0 No emulsion.

1 0n the basis of nonylphenol-polyglycol ether (having about 4 mols ofethylene oxide per mol of phenol).

lquelrls/butanolic solution of (mainly) benzene-sulionjc acid (alkali mea sa Upon addition of 0.1% of the compound a stable solubilized emulsionwas also obtained with half of the quantities of emulsilier I and II,which was not possible by addition of e cyrwo oNmcHmNwHmcmomo o o 9TABLE 1,.-YSU4RFACETENSI0N IN AQUEOUS SOLUTIONS Compound Surfacetension, dyn/cm.

TABLE 2.--IMMERSION WETTING POWER OF COTTON ACCORDING TO DIN 53,901

Sinking time [25 C. 1 g./l], sec. 25 C.

Sinldng time [g./l.] for 100 sec. at-

We claim:

1. Surface-active peruorated carboxylic :acid-amidamine derivatives andtheir quaternization products of the general formula in which Rfrepresents an unbranched perfluoro-alkyl group of 6 to 10 carbon atomsand Y represents a group of the following constitution in which n is -anumber from 1 to 4, z is 1 or 2, R represents a lower alkyl group IandXG represents -a halogen, sulfate or methosulfate anion.

2. A compound of the general formula `in which R, has the meaning givenin claim 1.

T0 3. A compound of the general formula 9 Rf-C ONE-(CHr-bl (CHzCHrOHhOle75 in which R, has the meaning given lin claim 1.

8 4. Acompound of the formula 3,577,447 5/1971 Sweeney et al. 260-40453,600,415 8/ 1971 Sweeney et Aa1 26o-404.5

CYFISCONHH)3N(CH2CH2OH)2 LEWIS GoTrs, Primary Examiner References Cited5 E" G- LOVE Assistant Exammer UNITED STATES PATENTS U.S.C1. X.R.

2,764,602 9/ 1956 Ahlbrecht 260-404.5 252-457; 260-561 HL, 501.13

